Acrylic acid nitrile

Santner H. J., Moller K. C., Ivanco J., Ramsey M. G., Netzer F. P., Yamaguchi S., Besenhard J. O., Winter M., Acrylic acid nitrile, a film-forming electrolyte component for lithium-ion batteries, which belongs to the family of additives containing vinyl groups, J. Power Sources, (2003) 119, 368-372. 

Presently, many organic additives fall into the category of polymerizable monomers. A non-exhaustive list includes esters (including carboxylic esters/carbonates and other inorganic esters such as phosphates, sulfates, and silicates) that are derived from vinyl and allyl alcohols [2,54,71], vinyl pyridine [63], acrylic acid nitrile [110], maleic acid derivatives [125, 131], vinyl sulfones [128], vinyl silanes [113], and isocyanates [65, 171] (Fig. 2). The synergistic effect of different unsaturated compounds used in various combinations has also been reported [1]. 

The 2-phenyl-2-ethyl-pentane-1,5-diacid-mononitrile-(1) of melting point 72° to 76°C, used as starting material in this process, can be produced for example from o-phenyl-butyric acid nitrile by condensation with acrylic acid methyl ester and subsequent hydrolysis of the thus-obtained 2-phenyl-2-ethyl-pentane-1,5-diacid-monomethyl ester-mononltrile-(l) of boiling point 176° to 185°C under 12 mm pressure. 

Acrylic Acid, CH2CHCOOH Free Radical Formers such as OH Ion Acrylic Acid Vapor 6000 kg/cm2 >75 Inhibitor—Methyl Ether of Hydroquinone-200ppm Storage in a cool, well ventilated area 18.5 429 Heterogeneous Free-Radical with a catalyst such as Azodiisobutyro-nitrile... 

Acryl amide is an important bulk chemical used in coagulators, soil conditioners and stock additives. The chemical synthesis has several drawbacks because the rate of acryl amide formation is lower than the formation of the by-product acrylic acid [54]. Further, the double bonds of the reactants and products cause by-product formations as well as formation of polymerization products. As a result of optimization with methods of molecular engineering, a very high activity of the biocatalyst nitrile hydratase at low temperature is yielded, enabling a successful biotransformation that is superior to the chemical route. Here, the synthesis is carried out at a low temperature of about 5°C, showing a conversion of 100%. 

Dipolar addition is closely related to the Diels-Alder reaction, but allows the formation of five-membered adducts, including cyclopentane derivatives. Like Diels-Alder reactions, 1,3-dipolar cycloaddition involves [4+2] concerted reaction of a 1,3-dipolar species (the An component and a dipolar In component). Very often, condensation of chiral acrylates with nitrile oxides or nitrones gives only modest diastereoselectivity.82 1,3-Dipolar cycloaddition between nitrones and alkenes is most useful and convenient for the preparation of iso-xazolidine derivatives, which can then be readily converted to 1,3-amino alcohol equivalents under mild conditions.83 The low selectivity of the 1,3-dipolar reaction can be overcome to some extent by introducing a chiral auxiliary to the substrate. As shown in Scheme 5-51, the reaction of 169 with acryloyl chloride connects the chiral sultam to the acrylic acid substrate, and subsequent cycloaddition yields product 170 with a diastereoselectivity of 90 10.84... 

Abstract. Auto-accelerated polymerization is known to occur in viscous reaction media ("gel-effect") and also when the polymer precipitates as it forms. It is generally assumed that the cause of auto-acceleration is the arising of non-steady-state kinetics created by a diffusion controlled termination step. Recent work has shown that the polymerization of acrylic acid in bulk and in solution proceeds under steady or auto-accelered conditions irrespective of the precipitation of the polymer. On the other hand, a close correlation is established between auto-acceleration and the type of H-bonded molecular association involving acrylic acid in the system. On the basis of numerous data it is concluded that auto-acceleration is determined by the formation of an oriented monomer-polymer association complex which favors an ultra-fast propagation process. Similar conclusions are derived for the polymerization of methacrylic acid and acrylonitrile based on studies of polymerization kinetics in bulk and in solution and on evidence of molecular associations. In the case of acrylonitrile a dipole-dipole complex involving the nitrile groups is assumed to be responsible for the observed auto-acceleration. 

Many substituents stabilize the monomer but have no appreciable effect on polymer stability, since resonance is only possible with the former. The net effect is to decrease the exothermicity of the polymerization. Thus hyperconjugation of alkyl groups with the C=C lowers AH for propylene and 1-butene polymerizations. Conjugation of the C=C with substituents such as the benzene ring (styrene and a-methylstyrene), and alkene double bond (butadiene and isoprene), the carbonyl linkage (acrylic acid, methyl acrylate, methyl methacrylate), and the nitrile group (acrylonitrile) similarly leads to stabilization of the monomer and decreases enthalpies of polymerization. When the substituent is poorly conjugating as in vinyl acetate, the AH is close to the value for ethylene. 

PAN was for a long time thought to be resistant to microbial attack. However, various bacteria that produced nitrile-converting enzymes were isolated from waste-waters of factories producing PAN fibre. Eor example, a nitrile hydratase/amidase enzyme system was studied from Mesorhizobium sp. E28 [68]. Also, bacteria (namely Ralstonia solanacearum and Acidovorax avenae) were used for the removal of acrylic acid from such waste-waters [69]. Later, on the basis of NMR... 

Feng YS, Chen PC, Wen FS et al (2008) Nitrile hydratase from Mesorhizobium sp F28 and its potential for nitrile biotransformation. Process Biochem 43 1391-1397 Wang CC, Lee CM, Wu AS (2009) Acrylic acid removal from synthetic wastewater and industrial wastewater using Ralstonia solanacearum and Acidovorax avenae isolated from a wastewater treatment system manufactured with polyacrylonitrile fiber. Water Sci Technol 60 3011-3016... 

The microorganism used has a high endogenous nitrile hydratase ratio when urea was used as an inducer in the presence of cobalt ions. (The nitrilase is undesirable as it converts the acrylamide further into acrylic acid). 

Catalytic oxidation and ammoxidation of lower olefins to produce a,/3-unsaturated aldehyde or nitrile are widely industrialized as the fundamental unit process of petrochemistry. Propylene is oxidized to acrolein, most of which is further oxidized to acrylic acid. Recently, the reaction was extended to isobutylene to form methacrylic acid via methacrolein. Ammoxidation of propylene to produce acrylonitrile has also grown into a worldwide industry. 

Many substances can be partially oxidized by oxygen if selective catalysts are used. In such a way, oxygen can be introduced in hydrocarbons such as olefins and aromatics to synthesize aldehydes (e.g. acrolein and benzaldehyde) and acids (e.g. acrylic acid, phthalic acid anhydride). A selective oxidation can also result in a dehydrogenation (butene - butadiene) or a dealkylation (toluene -> benzene). Other molecules can also be selectively attacked by oxygen. Methanol is oxidized to formaldehyde and ammonia to nitrogen oxides. Olefins and aromatics can be oxidized with oxygen together with ammonia to nitriles (ammoxidation). 

The last of the direct methods for graft initiation in liquid phase presented in this review involves chemical additives. Either free radical or ionic initiators can be chosen. Benzoyl peroxide is reported for grafting styrene on Nylon fibers in methanol media (71,105-107), as well as vinyl acetate (106). Azoisobutyro-nitrile has been employed in systems where the graft monomer is styrene (71,106) or vinyl acetate (106). Redox systems involving hydrogen peroxide and monomers like styrene (106,108,109). vinyl acetate (106), acrylic acid (108,109), methyl... 

The reaction of a-oxo acids with nitriles in the presence of an add catalyst gives acylamino acrylic acid derivatives, which are then used to prepare a.P-didehydropeptidesJ85 861 The reaction proceeds with a high degree of purity and is less time consuming. The reaction takes place initially to give the imino chloride 26, which subsequently reacts with the enolic form of the oxo acid. Several a-haloacyl-DHAs 27 have been prepared (Scheme 9) from which the corresponding a-aminoacyl-DHA can be prepared by ammonolysis in aqueous ammonia. 

In the presence of water and excess nitrile a,a-bis(acetylamino) carboxylic acids are formed in very good yields, which can be converted into acylamino acrylic acids in a subsequent step. 

Carbon Chain Backbone Polymers. These polymers may be represented by (4) and considered derivatives of polyethylene, where n is the degree of polymerization and R is (an alkyl group or) a functional group hydrogen (polyethylene), methyl (polypropylene), carboxyl (poly(acrylic acid)), chlorine (poly(vinyl chloride)), phenyl (polystyrene) hydroxyl (poly(vinyl alcohol)), ester (poly(vinyl acetate)), nitrile (polyacrylonitrile), vinyl (polybutadiene), etc. The functional groups and the molecular weight of the polymers, control their properties which vary in hydrophobicity, solubility characteristics, glass-transition temperature, and crystallinity. 

ACRYLONITRILE. [CAS 107-13-1], Today over 90% of the approximately 4,000.000 metric tons of acrylonitrile (also called aciylic acid nitrile, propylene nitrile, vinyl cyanide, and propenoic acid nitrile) produced worldwide each year use the Soldo-developed ammoxidation process. Acrylonitrile is among the top 50 chemicals producedin the United States as aresult of the tremendous growth m its use as a starting material for a wide range of chemical and polymer products. Acrylic fibers remain the largest use of acrylonitrile other significant uses are in resins and nitrile elastomers and as an intermediate in the production of adiponitnle and acrylamide. 

The hydrolysis of nitriles can be carried out with either isolated enzymes or immobilized cells. For example, resting cells of P. chlororaphis can accumulate up to 400 g/L of acrylamide in 8 h, provided acrylonitrile is added gradually to avoid nitrile hydratase inhibition (116). The degree of acrylonitrile conversion to acrylamide is 99% without any formation of acrylic acid. Because of its high efficiency the process has been commercialized and currendy is used by Nitto Chemical Industry Co. on a multithousand ton scale. 

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